Combined experimental and theoretical investigations of Ba3GaS4I: interesting structural transformation originated from halogen substitution. Issue 47 (21st November 2019)

• Record Type: Journal Article
• Authors: Li, Meng-Yue; Zhang, Yu-Xiao; Lin, Hua; Ma, Zuju; Wu, Xin-Tao; Zhu, Qi-Long
• Is Part Of: Dalton transactions. Volume 48:Issue 47(2019)
• Page Start: 17588
• Page End: 17593
• Publication Date: 2019-11-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt04033a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We have reported experimental and theoretical investigations of Ba3 GaS4 I and discussed the influences of halogen substitution on structural transformation and optical response changes. Abstract : Inorganic chalcohalides have emerged as promising functional materials for a range of applications. However, most of them are chlorides and bromides, while iodides are still rare. Herein, a new quaternary iodine-based chalcohalide Ba3 GaS4 I has been acquired by the reaction of BaS, Ga, S and BaI2 at 1173 K. Single-crystal XRD analysis reveals that Ba3 GaS4 I has a centrosymmetric structure (orthorhombic, space group Cmcm, a = 6.991(3) Å, b = 15.910(7) Å, c = 9.698(4) Å, V = 1078.6(7) Å 3, and Z = 4) and consists of isolated [GaS4 ] tetrahedra with charge-balanced Ba 2+ cations and I − anions. Ba3 GaS4 I can be regarded as the product of chemical substitution of Ba3 GaS4 X (X = Cl, Br), which adopts a different space group, Pnma . The influences of the halogen elements on the bandgap and birefringence have been discussed through first principles calculations and structural comparison.